Chlorination of Sulfides with Sulfuryl Chloride and Thionyl Chloride. I. Dimethyl Sulfide and Its Derivatives

133 Pages·7.4 MB·English

by  Birum, Gail H

P U R D U E U N IV E R S IT Y
THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION
Gail H. Birum___________________________
by____________________________________
Chlorination of Sulfides With Sulfuryl Chloride and
en titled
Thionyl Chloride* I . Dimethyl Sulfide and Its Derivatives^'
COMPLIES WITH THE UNIVERSITY REGULATIONS ON GRADUATION THESES
AND IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS
FOR THE DEGREE OF
_____________________Doctor of Philosophy_______________________
._____________________________________________________________P bofkssor in C harge o f T hesis
Head of School or D epartment
TO THE LIBRARIAN:-----
3»
THIS THESIS IS NOT TO BE REGARDED AS CONFIDENTIAL.
PHOFTseoK nr chasqb
GRAD. SCHOOL FORM 9

CHLORINATE ON OF SULFIDES WITH SULFURYL CHLORIDE AND THTONYL CHLORE DE.
I. DIMETHYL SULFIDE AND ITS DERIVATIVES
A Thesis
Submitted to the Faculty
of
Purdue University
by
Gail H. Birum
In Partial Fulfillment of the
Requirements for the Degree
of
Doctor of Philosophy
June, 19£L
ProQuest Number: 27714074
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ACKNOWLEDGEMENT
The author wishes to express his sincere appreciation to Professor
E. T. McBee and Professor William E. Truce, the directors of this re­
search, for their guidance and encouragement throughout the course of
this investigation.
Appreciation is also expressed to the Air Materiel Command, Wight
Field, Dayton, Ohio, and to the Purdue Research Foundation for the
financial assistance which made this work possible.
TABLE OF CONTENTS
Page
ABSTRACT.............................................................................».................... 1
INTRODUCTION............................ 1
DISCUSSION................... 3
Chlorination of Dimethyl Sulfide........................... 3
Chlorination of Dimethyl Sulfide With Sulfuryl Chloride.... 6
Chlorination of Dimethyl Sulfide With Thionyl Chloride..... 8
Chlorination of Dimethyl Sulfide With Chlorine............. 12
Chlorination of Trithiane With Sulfuryl Chloride and
Thionyl Chloride. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Identification of the Chlorodimethyl Sulfides.............. 15
Monochlorodimethyl sulfide• • .......................... 15
chlorodimethyl sulfide . . . . . . . . . . . . . . . . . . . 16
chlorodimethyl sulfide. . . . . . . . . . . . . . . . . . . . . . . . 17
°<f otjoC'-Trichlorodimethyl sulfide........................ 18
^«£c<-Trichlorodimethyl sulfide ........ ............... 18
od -Tetr achlorodimethyl sulfide .................... 19
od -Tetr achlorodimethyl sulfide . . . . . . . . . . . . . . . 20
Pent achlorodimethyl sulfide.. . . . . . . . . . . . . . . . . . . . . . . . 20
Hexachlorodimethyl sulfide.............................. 21
Chlorination of tyButyl Methyl Sulfide With Sulfuryl
Chloride and Thionyl Chloride ................ 22
Mechanism of Chlorination of Sulfides...................... 23
Oxidation of<k"Chlorosulfides to Sulfones 29
Preparation of Fluorodimethyl Sulfides From Chlorodimethyl
Sulfides...*. ........... 32
Oxidation of Fluorodimethyl Sulfides to Sulfones..... 35
Chlorination of Sulfones................................. 35
TABLE OF CONTENTS CONTINUED
Page
EXPERIMENTAL................................................ 37
Chlorination of Dimethyl Sulfide With Sulfuryl Chloride..*• 37
One and two-tenths moles of sulfuryl chloride per mole
of dimethyl sulfide................................... 37
One and five-tenths moles of sulfuryl chloride per mole
of dimethyl sulfide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
Two and twenty-five-hundredths moles of sulfuryl
chloride per mole of dimethyl sulfide. . . . . . . . . . . . . . . . . 39
Three and one-half moles of sulfuryl chloride per mole
of dimethyl sulfide..................................... 39
Four moles of sulfuryl chloride per mole of dimethyl
su lfid e......................* ........ ................ I4I
Four and one-half moles of sulfuryl chloride per mole
of dimethyl sulfide..................................... U3
Six moles of sulfuryl chloride per mole of dimethyl
sulfide... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . U5
Ten moles of sulfuryl chloride per mole of dimethyl
sulfide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . U6
Chlorination of <x,otrDichlorodimethyl Sulfide With Sulfuryl
Chloride........T .T ..... . . . . . . . . . . . . . . . . . . . . . . . ............ I48
Chlorination of oc,o£Ot-Trichlorodimethyl Sulfide With
Sulfuryl Chloride........................................ U9
Chlorination of ^oV-Tetrachlorodimethyl Sulfide With
Sulfuryl Chlo ri de.T.T.T. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . go
Chlorination of Dimethyl Sulfide With Thionyl Chloride..... 50
One and two-tenths moles of thionyl chloride per mole
of dimethyl sulfide................................... 5°
Two and two-tenths moles of thionyl chloride per mole
of dimethyl sulfide..................................... 52
Six moles of thionyl chloride per mole of dimethyl
sulfide....... .............. 52
Chlorination of Dimethyl Sulfide With Chlorine.................. 5U
Chlorination of Trithiane With Thionyl Chloride................ 55
TABLE OF CONTENTS CONTINUED
Page
Chlorination of Trithiane With Sulfuryl Chloride . . . . . . . . 56
Chlorination of ^ -Dichlorodimethyl Sulfide >h.th Sulfuryl
C h l o r i d e 61
1 -Tri chlorodimethyl sulfide . . . . . . . . . . . . . . . . . . . 61
-Tetrachlorodimethyl sulfide.................... 62
Treatment of o^oC1 -Dichlorodimethyl Sulfide With Thionyl
Chloride.....T. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6U
Treatment of c<, c<,p< 1 -TrIchlorodimethyl Sulfide With Thionyl
C h l o r i d e . 65
Chlorination of t-Butyl Methyl Sulfide With Thionyl Chloride 65
t—Butyl trichloromethyl sulfide.......................... 65
t-Butyl monoehloromethyl sulfide........................ 67
t-Butyl dichloromethyl sulfide........................... 67
Chlorin at i on of aL,<Xr-Di ch loro dimethyl Sulfide With Sulfuryl
Chloride in the Presence of Bromine. . . . . . . . . . . . . . . . . . . . . . 68
Oxidation of Sulfides to Sulfones........................... 68
Monochlorodimethyl sulfone. . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
ot,96rDichloro dimethyl sulf one . . . . . . . . . . . . . . . . . . . . . . . . . . 69
oj? —Di chlorodimethyl sulfone . . . . . . . . . . . . . . . . . . . . . . . . 69
-Trichlorodimethyl sulfone . . . . . . . . . . . . . . . . . . . . . 70
o<,o^of“Trichlorodimethyl sulfone*......... .. .... .. .... 71
erf, <g»Grf,a(' -Tetr achlorodimethyl sulfone ..................... 71
-Tetrachlorodimethyl sulfone .................... 72
Pentachlorodimethyl sulfone.............................. 72
Hexachlorodimethyl sulfone...... .......... ............. 73
t-Butyl trichloromethyl sulfone.......................... 73
TABLE OF CONTENTS CONTINUED
Page
Preparation of Fluorodimethyl Sulfides From Chlorodi­
methyl Sulfides .......... . . . . . . . . . . . 7h
«^et-Trifluorodimethyl sulfide................... . .. 7h
oC-Chloro<*-difluorodimethyl sulfide ... .. .. .. ..... 7U
oc1 -Chloro- ©g <3*rtrifluorodimethyl sulfi de............... 76
oij oc*-Dichloro-<X,<x~dif luorodimethyl sulfide ................76
Pent afluorodimethyl sulfide ............................. 77
Attempt to Prepare Monofluorodimethyl Suli^de.............. 77
Monochlorodimethyl sulfide and potassium fluoride In
ethylene glycol. . . . . . . 77
Mono chlorodimethyl sulfide and anhydrous potassium
fluoride. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Monochlorodimethyl sulfide and antimony trifluoride..... 79
Mono chlorodimethyl sulfide and silver fluoride. .. . .. . .. 80
Attempt to Prepare «,ot-Di fluorodimethyl sulfide............ 81
Attempt to Prepare 1 -Trifluorodimethyl Sulfide. . ...... 82
Attempt to Prepare -Tetrafluorodimethyl Sulfide... 82
Attempt to Prepare Hexafluorodimethyl Sulfide. ............ 83
Oxidation of Fluorodimethyl Sulfides to Sulfones.......... 8L
fluorodimethyl sulfone........... .......... .. 8U
<*-Chlor o -oc,btrdi fluorodimethyl sulfone ................... 85
©t-Chloro-ej, c^ortri fluorodimethyl sulfone . . . . . . . . . . . . . . 86
Treatment of Pentafluorodimethyl Sulfide With Chromic
A n h y d r i d e 87
Treatment of Dimethyl Sulfone With Sulfuryl Chloride and
Benzoyl Peroxide ........... 87
Treatment of Dimethyl Sulfone With Chlorine* . ................ 88
TABLE OF CONTENTS CONTINUED
Page
Treatment of Dimethyl Sulfone With Basic Sodium
Hypochlorite♦ 8 9
Treatment of Diethyl Sulfone With Sulfuryl Chloride and
Benzoyl Peroxide.......................................... 89
BIBU OGRAPHY......................................... 91
VITA